Chloro-aryloxy alkanes



Patented Apr. 4, 1950 7 2,503,207 I CHLOR'O -ARYLOXY Clarence L. Moyle,Clare, Mich, assignor to The Dow Chemical Company, Midland, Mich acorporation of Delaware No Drawing. Application September-18, 1946,Serial No. 691,831

This invention is directed to new compounds characterized aschloro-arylox'y alkane's, having the formula: I y

lli

C n R Cl" wherein R and R represent hydrogen or a lower alkyl radical, Xis hydrogen or phenyl, and n is the integer 1 or 2. The expression loweralkyl refers to alkyl radicals containing not more than carbon atoms andpreferably 1 or 2 carbon atoms. The compounds are useful as modifiers inplastic compositions, as parasiticides and as intermediates for thepreparation of more complex compounds. The compounds are liquids orsolids, almost insoluble in water but somewhat soluble in many organicsolvents.

The compounds of the invention may be prepared by reacting a salt of a'chloro-phenol with'a 4'Claims. (o1. zoo-413) dihalomethane or higherdihaloalkane having both halogen substituents attached to the"sainecarbon atom, e. g., 1.1-dichloro-ethane, 1.1-dibromoethane,1.1-dichloropropane, 2.2-dichlor0- propane, etc. Conveniently the sodiumsalt of the chloro-phenol is employed, which may be prepared by reactingequimolecularproportions of I sodium and the chloro-phenol in a solvent,such as ethanol or toluene. To this is then added a one-half molecularproportion of the dihalo alkane, and the mixture is then heated under.

46 grams (2 mols) of sodium was dissolved under reflux in 500 grams ofabsolute alcohol. 326 grams (2 mols) of 2.4-dichlorophenol was added tothe alcoholic solution to form the sodium salt of the phenol. 85 grams(1 mol) of dichloromethane was then mixed with the solution of thesodium phenolate and the mixture was heated in an autoclave at about 110C. for 8 hours. The reactor and contents were then cooled and thereaction mixture was discharged into a body of water. The organicreaction product was separated from the water by extraction with benzeneand the benzene extract was fractionally distilled under reducedpressure. There was obtained 149 grams of di-(2.4-dichlorophenoxy)-methane as a pale yellow solid melting at 96-98 0., and boiling at213-216 C. at 6 mm. pressure. The formula is:

Example 2 23 grams of -s'odiu'm was reacted with 1285 grams of4-chl'oro-phenol in 145 grams of methanal. :52 grams "of1.1-dich1oroethane (ethylid'ene chloride) was added to the alcoholicpheno'la't'e solution and the resulting solution was heated at about 125C. under autogenous pressure for 12 hours. The reaction mixture was thendiluted with 400 grams of water and heated at atmospheric pressure toevaporate and recover the alcohol. 108 grams of an insoluble oilseparated [from the aqueous solution, which was washed successively withwater and with dilute sulphuric acid. On fractional distillation of theoil there was-obtained grams of 1.1-di-(4-chloro-phenoxy)-ethane,boiling at 180-184 C. at 4 mm. pressure. The formula is:

In similar manner di l-chloro-phenoxy) methane was obtained froml-chloro-phenol and dichloromethan'e. which is a pale yellow solidmelting at 67-69 C. and boiling at 189-194 C. at 6mm. pressure. Theformula is:

Di- (2-phenyl-fi chloro-phenoxy) -methane was 1 preparedfrom-2-phenyl-6-chloro-phenol and dichloromethane, a white crystallinesolid when crystallized from petroleum ether, melting at 92- 93.5 C. Theformula is:

Other chloro-aryloxy alkanes within the scope of the invention are madeby reacting a chlorophenolate with such alkylidene halides as1.1-dichloropropane, 2.2-dich1oropropane, 1.1-dichloron-butane,2.2-dichloro-n-butane, 1.1-dich1oro-2- methyl-propane,1.1-dichloro-n-pentane, 1.1-dichloro-n-hexane, etc., and with thecorresponding bromo-derivatives.

My new compounds have been found to possess a high degree of toxicityagainst many insect pests, and can be used in lethal concentrationswithout, or with negligible, injury to the foliage of plants to whichthe insecticidal compositions are applied. For use as an insecticide thecompounds may be mixed with a finelydivided solid carrier as a drymixture. Such mixture may be suspended in water, with the aid of awetting agent, if desired, and the suspension applied in the form of aspray to the plants. Suitable concentration of the toxicant in suchwater sus- 4 This application is a continuation-in-part of my priorapplication, Serial No. 441,377, filed May 1; 1942, now abandoned.

pensions is on the order of about 0.5 to 2 pounds I claim: per 100gallons of the spray mixture. In partic- 5 1. A chloro-phenoxy alkanehaving the ular, the new compounds have been found to be formula: highlyeffective against Mexican bean beetle.

To demonstrate their toxicity, tests were made X R X on third instarMexican bean beetle and red spider OALOG adults. A dry mixture wasprepared composed C n t, C1 of parts by weight of the toxicant and 80parts of diatomaceous earth. The mixt' re was diswherein R and R eachrepresent one of the group g gg gjfg 2? 5835325 32; f i 2 3: consistingof hydrogen and lower alkyl, X is one 1 0 and 2 5 of the 0X1 g y of thegroup consisting of hydrogen and phenyl,

and n is an integer from 1 to 2, inclusive. gallons of the spray, with0.25 pound of sodium 7 2.D1-(2.4-d1chloro-phen0xy)-methane. laurylsulphate per 100 gallons added as dispers- 3 1 4 chloro henox eth ne ingagent. These spray mixtures were applied in i ox f g usual manner forthe control of the indicated p y plant pests with results as shown inthe table: 0' CLARENCE L. MOYLE.

i P c t 'loxicant gggg' Organism ll ngilag Kill 1.1-di-(4-chlorophenoxy)-etl1ane 2.0 Mexican Bean I i e etle (3rd instar) 0 100 Do 1.5 do 0 100Do 1.0 .d0 o 100 D0 2.0 Red Spider (adult) 0 100 Di-(lechlorophenoxy)-methaue 2.0 Mexican Bean Beetle (3rd instar) 0 100 Do1.5 0 100 Do. 1.0 (1 o 7 Dow 2.0 Red Spider (adult) O 99 file of thispatent:

UNITED STATES PATENTS Number Name 7 Coleman Sept. 20, 1938 Date OTHERREFERENCES Birosel, Philippine Jour. Science, v01. 34 (1927), pages157-160, abstracted in Chem. Abs,

vol. 22, (1928) page 766.

Tornow et al., Ber. der. Deut. Chem. Ges., vol. 62B (1929) pages2844-2850. I

1. A CHLORO-PHENOXY ALKANE HAVING THE FORMULA: